JP2018008405A - Method for producing amorphous thermoplastic resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an amorphous thermoplastic resin film which can expect enhancement of slidability of an amorphous thermoplastic resin film without lowering mechanical properties, electrical properties and heat resistance, and can be easily produced without damaged.SOLUTION: A method for producing an amorphous thermoplastic resin film 4 having a glass transition point of 200°C or higher by a molding method using a molding material 1 includes: preparing a molding material 1 from 100 pts.mass of an amorphous thermoplastic resin having a glass transition point of 200°C or higher and 0.1-20 pts.mass hydrophobic silica spherical fine particles contributive to slidability; setting a water content of the molding material 1 at 2,000 ppm or less; charging the molding material 1 to a melt extrusion molding machine 20 to continuously subject a thin amorphous thermoplastic resin film 4 to melt extrusion molding from a dice 23; and winding the amorphous thermoplastic resin film 4 around a pair of pressure bonding rolls 26, a cooling roll 27 and a winding tube 29 positioned at the downstream of them.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for producing a non-crystalline thermoplastic resin film used as a base film for a speaker diaphragm, a film for insulation coating of electric wires, a base film for film capacitors, and a base film for various tapes. More specifically, the present invention relates to an improvement in slipperiness and the like of an amorphous thermoplastic resin film.

  Amorphous thermoplastic resins having a glass transition point (Tg) of 200 ° C. or higher, such as polyetherimide (PEI) resin, polyethersulfone (PES) resin, or polyphenylsulfone (PPSU) resin, are mechanically It has excellent properties such as properties, heat resistance, flame retardancy, dimensional stability, and electrical characteristics. In view of this point, amorphous thermoplastic resin films obtained from these resins include base film for speaker diaphragms, insulating film for electric wires, base film for film capacitors, and base materials for various tapes. It is used as a film.

  However, since the amorphous plastic resin film is usually inferior in slipperiness (also referred to as slidability), for example, a film having a thickness of 500 μm or less may be hindered in winding of the film, slit formation, etc. Work may become difficult and wrinkles may occur on the film. There may also be a problem that the film is torn, the film is torn, or the roll is inappropriately wound. Therefore, it is necessary to improve the slipperiness (slidability) of the amorphous thermoplastic resin film.

  In general, as a method for improving the slipperiness of the resin film, (1) a method of forming fine irregularities on the surface of the resin film to reduce the friction coefficient of the surface, (2) silicon dioxide particles, calcium carbonate particles, kaolin Particles, inorganic particles such as alumina oxide particles, silicone particles, cross-linked polystyrene particles, cross-linked epoxy particles, cross-linked acrylic particles and other organic particles are added to form fine protrusions on the surface of the resin film. Method for reducing friction resistance on film surface and improving slipperiness (see Patent Document 1), (3) Glycerin such as glycerin monobehenate or glycerin monostearate, and fatty acid monostearate having 20 or more carbon atoms Method of adding rate (see Patent Document 2), (4) Silicone rubber to thermoplastic resin (see Patent Document 3) ), Or fluorine resin (added see Patent Document 4) small compound coefficient of friction, etc., a method of reducing the surface friction coefficient and the like by melt extruding a resin film.

JP-A-6-31453 JP 2008-308606 A Japanese Patent No. 4980205 Japanese Patent No. 5241470

  However, in the case of the method (1), since the formation of mere fine irregularities is stopped, the slipperiness of the surface of the resin film becomes insufficient. In the case of the method (2), inorganic particles such as silicon dioxide particles, calcium carbonate particles, kaolin particles and alumina oxide particles, silicone particles, crosslinked polystyrene particles, crosslinked epoxy particles, crosslinked acrylic particles, etc. Since the organic particles have high cohesiveness and poor dispersibility, they are not uniformly dispersed in the resin film but become aggregates (dama), resulting in a problem that the mechanical properties of the resin film are deteriorated.

  In the case of the method (3), it can be used for a resin having a melt molding temperature of 300 ° C. or lower, such as a polycarbonate resin, but a polyetherimide resin, a polyethersulfone resin, a polyphenylsulfone resin, etc. When the amorphous thermoplastic resin has a glass transition point exceeding 200 ° C., the molding temperature exceeds 300 ° C., so that glycerin and fatty acid monostearate having 20 or more carbon atoms are decomposed during melt molding. Or it may volatilize. In addition, there may be a problem of bleeding and migration from the resin film after melt extrusion molding.

  In the case of the method (4), a silicone rubber is added to an amorphous thermoplastic resin such as a polyetherimide resin, a polyether sulfone resin, or a polyphenyl sulfone resin whose melt molding temperature exceeds 300 ° C., When melt extrusion molding, a part of the silicone rubber remains in the melt extrusion molding machine, and this residue undergoes a cross-linking reaction with oxygen in a high-temperature atmosphere where oxygen is present. This leads to the generation of a low molecular composition by the cleavage of the molecular chain. When the gel is generated, a new problem arises in that a hole is formed in the resin film from the gel portion, or the resin film is cut off from the hole-opened portion and cannot be wound.

  In addition, even if the resin film can be wound up, because of the foreign matter remaining in the resin film, when the resin film is manufactured, troubles in the winding process, defects in quality, and long run moldability are reduced. Or the gel-like part may be convex, resulting in poor appearance. Further, when the low-molecular product is in a liquid state, problems such as bleeding and migration from the resin film after melt extrusion molding occur.

  Further, in Patent Document 4 of (4), a fluororesin having a melting temperature of 120,000 poise or less is added to a polyetherimide resin, and fine unevenness is transferred to the resin film to improve the slipperiness of the resin film. A method is described. The fluororesin used in this method is of two types, a polytetrafluoroethylene-hexafluoropropylene copolymer and a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer.

  When these two types of fluororesins are added to a polyetherimide resin to prepare a molding material, and a resin film having a thickness of 500 μm or less is produced by a melt extrusion molding method using the molding material, Since the effect of improving the slipperiness of the resin is small, in order to improve the slipperiness, a large amount of two kinds of fluororesins must be added. A molding material obtained by adding a large amount of two types of fluororesin to a polyetherimide resin reduces the quantitative supply of the molding material to a melt extrusion molding machine, which may make it difficult to mold a resin film. In addition, since the compatibility between these two types of fluororesin and polyetherimide resin is not good, problems such as hole opening may occur in the resin film.

  In addition, since the two types of fluororesins are inferior in uniform dispersibility in the polyetherimide resin, it becomes difficult to impart uniform slipperiness to the resin film, and the mechanical strength is reduced and the holes are opened. Problems arise. Further, when a fluororesin is used as an additive, it is necessary to use a corrosion-resistant steel material for a member such as a melt-extrusion molding machine or a die, which increases the cost, and as a result, the resin film becomes expensive. There's a problem.

  The present invention has been made in view of the above, and can improve the slipperiness of the amorphous thermoplastic resin film without deteriorating mechanical properties, electrical properties, heat resistance, etc. It aims at providing the manufacturing method of the amorphous thermoplastic resin film which can be manufactured easily without damaging a thermoplastic resin film.

  As a result of diligent research to solve the above problems, the present inventors have focused on hydrophobic silica spherical fine particles having low agglomeration and high dispersibility, and the hydrophobic silica spherical fine particles and the amorphous thermoplastic resin The present invention was completed by preparing a molding material according to the above, and melt-extruding an amorphous thermoplastic resin film with the molding material.

That is, in order to solve the above-mentioned problems in the present invention, an amorphous heat for producing an amorphous thermoplastic resin film having a glass transition point of 200 ° C. or higher by a molding method using a predetermined resin-containing molding material. A method for producing a plastic resin film, comprising:
The molding material contains 100 parts by mass of an amorphous thermoplastic resin having a glass transition point of 200 ° C. or higher, and 0.1 to 20 parts by mass of hydrophobic silica spherical fine particles, and has a water content of 2000 ppm or less,
The molding material is put into an extrusion machine for film, and an amorphous thermoplastic resin film is continuously melt-extruded from the die, and the temperature of the extruder and the die during the melt-extrusion molding is changed to amorphous. The glass transition point of the thermoplastic resin to the glass transition point + 200 ° C., and the melt-extruded amorphous thermoplastic resin film is wound around a pressure roll, a cooling roll, and a winding tube located downstream of these, It is characterized in that the temperature of at least one of the pressure-bonding roll and the cooling roll is in the range of 50 ° C. to the glass transition point of the amorphous thermoplastic resin + 50 ° C.

An amorphous thermoplastic resin having a glass transition point of 200 ° C. or higher is introduced into a melt kneader for molding material and melted. Then, hydrophobic silica spherical fine particles are introduced into the melt kneader to be amorphous. A molding material can be prepared by melt-kneading with a thermoplastic resin, and then the prepared molding material can be put into an extruder for film.
Also, the melt kneader for the molding material is provided with an inlet for the amorphous thermoplastic resin, and a side feeder for introducing hydrophobic silica spherical fine particles located downstream from the inlet. can do.

Further, the temperature when the hydrophobic silica spherical fine particles are introduced and melt-kneaded with the amorphous thermoplastic resin can be set in the range of the glass transition point of the amorphous thermoplastic resin to the glass transition point + 200 ° C.
Also, hydrophobic silica spherical fine particles are put into a melt kneader and melt kneaded by stirring and mixing with an amorphous thermoplastic resin at room temperature, and the temperature at the time of melt kneading is set to a glass of amorphous thermoplastic resin. It is possible to set it as the range of a transition point-glass transition point +200 degreeC.

In addition, the slip property of the amorphous thermoplastic resin film cooled by the cooling roll is set to 1.0 or less in terms of the static friction coefficient (μs), 1.0 or less in terms of the dynamic friction coefficient (μk), and the mechanical properties are set to the tensile strength. 50 N / mm ² or more, elongation at break at 50% or more, heat resistance at 200 ° C. or more at the first inflection point of storage elastic modulus (E ′), and electrical characteristics at 250 V / in dielectric breakdown voltage. It is preferable that the acoustic characteristics be 0.015 or more in terms of loss tangent at 20 ° C. or more.

  Here, the “spherical shape” of the hydrophobic silica spherical fine particles of the molding material in the claims includes both a true sphere shape and a slightly distorted sphere shape. An inlet for the amorphous thermoplastic resin is provided upstream of the melt kneader for the molding material, and a side feeder for introducing hydrophobic silica spherical fine particles is provided on the middle and downstream sides of the melt kneader. Can be provided. In addition, the amorphous thermoplastic resin film can be used as at least a base film for a diaphragm of a speaker, an insulating coating film for an electric wire, a base film for a film capacitor, and a base film for various tapes. .

  The number of pressure-bonding rolls and cooling rolls can be increased or decreased as necessary. At least one of a concave portion and a convex portion for transfer is formed on the peripheral surface of at least one of the pressure roll and the cooling roll, and amorphous thermoplasticity is formed by at least one of the concave portion and the convex portion. A plurality of concave portions or convex portions can be formed on at least one of the front and back surfaces of the resin film. A slitting blade for cutting a film is arranged between the crimping roll and the winding tube, and a rotatable tension roll for applying tension to the amorphous thermoplastic resin film between the winding tube and the slitting blade. Can be provided.

  According to the present invention, as a molding material, an amorphous thermoplastic resin having a glass transition point of 200 ° C. or higher is used instead of a simple amorphous thermoplastic resin, so that heat resistance is improved. Can do. Moreover, since the hydrophobic silica spherical fine particles are contained in the molding material, the slipperiness of the amorphous thermoplastic resin film can be improved.

  According to the present invention, there is an effect that the slipperiness of the amorphous thermoplastic resin film can be improved without deteriorating mechanical properties, electrical properties, heat resistance and the like. Moreover, it can manufacture easily, without damaging an amorphous thermoplastic resin film.

According to the second aspect of the invention, the hydrophobic silica spherical fine particles can be uniformly dispersed in the amorphous thermoplastic resin.
According to the invention described in claim 3, when the fine hydrophobic silica spherical fine particles are introduced into the melt-kneader for the molding material, the fine hydrophobic silica spherical fine particles are prevented from rising and workability and environmental performance are improved. Can be made.

  According to the invention described in claim 4, it is possible to obtain an amorphous thermoplastic resin film excellent in slipperiness, mechanical characteristics, electrical characteristics, heat resistance and the like. Moreover, it becomes possible to satisfy the electrical characteristics when the amorphous thermoplastic resin film is used as a base film for a film capacitor or the like. Furthermore, it is possible to satisfy the acoustic characteristics when the amorphous thermoplastic resin film is used as a base film for a speaker diaphragm.

It is explanatory drawing which shows typically the melt-kneader for the molding materials in embodiment of the manufacturing method of the amorphous thermoplastic resin film which concerns on this invention. It is explanatory drawing which shows typically the melt extrusion molding machine in embodiment of the manufacturing method of the amorphous thermoplastic resin film which concerns on this invention. It is explanatory drawing which shows the 1st inflexion temperature of the storage elastic modulus in the Example and comparative example of the manufacturing method of the amorphous thermoplastic resin film which concerns on this invention.

  Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. The method for producing an amorphous thermoplastic resin film in the present embodiment is at least amorphous thermoplastic as shown in FIG. 1 and FIG. Hydrophobic silica spherical fine particles 3 are added to the resin 2 and the molding material 1 is prepared by a melt kneader 10. The crystalline thermoplastic resin film 4 is melt-extruded, and the amorphous thermoplastic resin film 4 is wound around a pair of pressure-bonding rolls 26, a cooling roll 27, and a take-up tube 29, and an amorphous thermoplastic resin is wound. The film 4 is sandwiched between the pressure roll 26 and the cooling roll 27 to produce the amorphous thermoplastic resin film 4 having excellent slipperiness.

  The molding material 1 includes an amorphous thermoplastic resin 2 having a glass transition point (Tg) of 200 ° C. or higher and hydrophobic silica spherical fine particles 3 that contribute to slipperiness, and these amorphous thermoplastic resin 2 and hydrophobicity It is prepared by melting and kneading the silica spherical fine particles 3. The amorphous thermoplastic resin 2 of the molding material 1 is not particularly limited as long as it is an amorphous thermoplastic resin having a glass transition point of 200 ° C. or higher. Examples thereof include a sulfone resin or a polyphenylsulfone resin, and may be any of powder, granules, flakes, and pellets. The amorphous thermoplastic resin 2 can be used alone or blended.

  Specific examples of the polyetherimide resin include ULTEM 1000-1000-NB [SABIC, which is produced from a polycondensate of 4,4 ′-[isopropylidene (p-phenyllenoxy) diphthalic acid] and m-phenylenediamine. Innovative Plastics product name], ULTEM 1010-1000-NB [SABIC Innovative Plastics product name], ULTEM 9011-1000-NB [SABIC Innovative Plastics product name], 4,4 '-[Isopropi ULTEM CRS5001-1000-NB [product name made by SABIC Innovative Plastics] manufactured from a polycondensate of redene (p-phenyllenoxy) diphthalic acid] and p-phenylenediamine. Examples of the method for producing the polyetherimide resin include the methods described in JP-B-57-9372 and JP-A-59-80067.

  As the polyetherimide resin, a block copolymer, a random copolymer, and a modified body with other copolymerizable monomers can be used as long as the effects of the present invention are not impaired. For example, ULTEM XH6050-1000 [a product name manufactured by SABIC Innovative Plastics Co., Ltd.], which is a polyetherimide sulfone copolymer, can be used. This polyetherimide resin may be used alone or in combination of two or more.

  Specific examples of the polyethersulfone resin include Sumika Excel PES (product name, manufactured by Sumitomo Chemical Co., Ltd.), Veradel polyethersulfone (product name, manufactured by Solvay Specialty Polymers), or Ultrason E (product name, manufactured by BASF). ] And the like. As the polyethersulfone resin, a block copolymer, a random copolymer, and a modified body with other copolymerizable monomers can be used within a range not impairing the effects of the present invention.

  Examples of the polyphenylsulfone resin include resins described in JP-T-2009-530461. Specific examples of this polyphenylsulfone resin include Radel polyphenylsulfone [product name manufactured by Solvay Specialty Polymers] or Ultrason P [product name manufactured by BASF]. The method for producing the polyphenylsulfone resin is not particularly limited. For example, U.S. Pat. No. 3,634,355, U.S. Pat. No. 4,008,203, U.S. Pat. , 108,837, U.S. Pat. No. 4,175,175 and the like. As the polyphenylsulfone resin, a block copolymer, a random copolymer, and a modified body with other copolymerizable monomers can be used within a range not impairing the effects of the present invention.

Examples of the hydrophobic silica spherical fine particles 3 include fine silica spherical fine particles described in, for example, Japanese Patent No. 4579265, Japanese Patent No. 592938, Japanese Patent No. 516836, and the like. The fine hydrophobic silica spherical fine particles 3 include hydrophilic spheres substantially composed of SiO ₂ units obtained by hydrolysis and condensation of a tetrafunctional silane compound and / or a partial hydrolysis condensation product thereof. A step of introducing R ¹ SiO _3/2 units (wherein R ¹ is a substituted or unsubstituted monovalent carbon hydrogen group having 1 to 20 carbon atoms) onto the surface of the silica fine particles, and then R ² ₃ SiO _{1 / 2} units (wherein R ² is the same or different and is a substituted or unsubstituted monovalent carbon hydrogen group having 1 to 6 carbon atoms), and a hydrophobic silica sphere obtained by hydrophobic treatment Fine particles are optimal.

The hydrophobic silica spherical fine particles 3 are “substantially composed of SiO ₂ units”, but the hydrophobic silica spherical fine particles 3 are basically composed of SiO ₂ units, but are composed only of these units. Rather, it means having at least a large number of silanol groups on the surface. In some cases, the tetrafunctional silane compound as a raw material and / or a hydrolyzable group (hydrocarboxy group) derived from the partial hydrolysis-condensation product thereof is not converted into a silanol group in a small amount as it is. This means that it may remain on the surface or in the interior.

  Specific examples of the hydrophobic silica spherical fine particles 3 include X-24-9163A (product name manufactured by Shin-Etsu Chemical Co., Ltd.), X-24-9600A-80, which has a highly hydrophobic surface and is excellent in dispersibility and adhesion. [Product name manufactured by Shin-Etsu Chemical Co., Ltd.], X-24-9404 [Product name manufactured by Shin-Etsu Chemical Co., Ltd.], and the like. A method for producing the hydrophobic silica spherical fine particles 3 is not particularly limited, and a method described in Japanese Patent No. 4579265 may be mentioned.

  The average particle diameter of the hydrophobic silica spherical fine particles 3 is 5 nm to 1000 nm, preferably 3 nm to 500 nm, more preferably 30 nm to 250 nm. This is because when the average particle diameter of the hydrophobic silica spherical fine particles 3 is less than 5 nm, the hydrophobic silica spherical fine particles 3 are aggregated, and the uniform dispersibility in the amorphous thermoplastic resin film 4 is lowered, resulting in agglomeration. It is because it becomes a collection (dama) and, as a result, the mechanical characteristic of the amorphous thermoplastic resin film 4 deteriorates. Moreover, it is because melt viscosity increases and the moldability of the amorphous thermoplastic resin film 4 falls.

  On the other hand, when the average particle diameter of the hydrophobic silica spherical fine particles 3 exceeds 1000 nm, the mechanical properties of the amorphous thermoplastic resin film 4 are deteriorated or extruded from the die 23 of the melt extrusion molding machine 20. This is because the melt elongation of the band-shaped amorphous thermoplastic resin film 4 is lowered and the moldability of the amorphous thermoplastic resin film 4 is lowered.

  The spherical shape of the hydrophobic silica spherical fine particles 3 may be a true sphere or a slightly distorted sphere. The shape of the hydrophobic silica spherical fine particles 3 is evaluated by the circularity when the hydrophobic silica spherical fine particles 3 are projected two-dimensionally, and the circularity is in the range of 0.8 to 1. This circularity is measured by image analysis of a particle image obtained with an electron microscope, and is represented by a circle circumference length / particle circumference length equal to the particle area.

  The addition amount of the hydrophobic silica spherical fine particles 3 is 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1.0 to 10 parts by weight with respect to 100 parts by weight of the amorphous thermoplastic resin. Good part. This is because sufficient slipperiness cannot be imparted to the amorphous thermoplastic resin film 4 when the added amount of the hydrophobic silica spherical fine particles 3 is less than 0.1 parts by mass. On the contrary, when the amount of the hydrophobic silica spherical fine particles 3 added exceeds 20 parts by mass, the slipping property becomes excessive and the mechanical properties are deteriorated. In addition, draw resonance occurs and the amorphous thermoplastic resin film 4 having a uniform thickness cannot be obtained, and the melt elongation is lowered, making it difficult to form the amorphous thermoplastic resin film 4. Based on why.

  Such a molding material 1 includes a polyolefin resin such as a polyethylene (PE) resin, a polypropylene (PP) resin, a polymethylpentene (PMP) resin, a polystyrene (PS) resin, polyethylene, and the like, as long as the characteristics of the present invention are not impaired. Polyester resin such as terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polyimide resin such as polyimide (PI) resin, polyamideimide (PAI) resin, polyamide 4T (PA4T) resin, Polyamide 6T (PA6T) resin, modified polyamide 6T (modified PA6T) resin, polyamide 9T (PA9T) resin, polyamide 10T (PA10T) resin, polyamide 11T (PA11T) resin, polyamide 6 (PA6) resin, polyamide 6 (PA66) resin, polyamide resin such as polyamide 46 (PA46) resin, polyetherketone (PEK) resin, polyetheretherketone (PEEK) resin, polyetherketoneketone (PEKK) resin, polyetheretherketoneketone (PEEKK) Polyaryl ketone resin such as resin, polyphenylene sulfide (PPS) resin, polyphenylene sulfide ketone resin, polyphenylene sulfide sulfone resin, polyarylene sulfide resin such as polyphenylene sulfide ketone sulfone resin, polytetrafluoroethylene (PTFE) resin (tetrafluoroethylene) Resin), polytetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) resin (ethylene tetrafluoride-perfluoroalkyl vinyl) -Terpolymer resin), tetrafluoroethylene-hexafluoropyrene copolymer (FEP) resin (also called tetrafluoroethylene-hexafluoropropylene copolymer resin), tetrafluoroethylene-ethylene copolymer ( ETFE) resin (also referred to as tetrafluoroethylene-ethylene copolymer resin), polychlorotrifluoroethylene (PCTFE) resin (also referred to as trifluorochloroethylene resin), polyvinylidene fluoride (PVdE) resin (fluorinated) Fluorine resin such as vinylidene fluoride / tetrafluoroethylene / hexafluoropyrene copolymer resin, polycarbonate (PC) resin, polyarylate (PAR) resin, polyacetal (POM) resin, liquid crystal polymer (LCP) Can add aliphatic polyketone resin it can.

  In addition, the molding material 1 includes an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, a lubricant, a flame retardant, an antistatic agent, and a heat resistance improver in addition to the above-described resin, as long as the characteristics of the present invention are not impaired. Further, a nucleating agent, an inorganic compound, an organic compound, etc. can be selectively added.

  In the above, when producing the amorphous thermoplastic resin film 4, first, the molding material 1 is prepared by melt-kneading the amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3, and this molding is performed. The material 1 is put into a film melt extrusion molding machine 20 to produce a thin amorphous thermoplastic resin film 4 having a thickness of 150 μm or less, for example, 3 to 100 μm. As a method for preparing the molding material 1, (1) the amorphous thermoplastic resin 2 is put into the melt kneader 10 for the molding material 1 and melted, and then the hydrophobic silica spherical fine particles 3 are put into the melt kneader 10. A method of preparing the molding material 1 by melting and kneading with the amorphous thermoplastic resin 2 that has been charged and melted. (2) The amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3 are mixed with a stirring mixer. A method of preparing the molding material 1 by stirring and mixing at room temperature (about 0 to 50 ° C.) and then melt extrusion kneading with the melt kneader 10 can be mentioned.

  These preparation methods may be any of the methods (1) and (2), but it is necessary to uniformly disperse the hydrophobic silica spherical fine particles 3 in the amorphous thermoplastic resin 2, and the hydrophobic silica spherical fine particles 3 From the viewpoint of preventing work-up and improving workability and environmental performance, the preparation method (1) is preferred.

  First, the preparation method of (1) will be described in detail. In this method, a Banbury mixer, a mixing roll, a pressure kneader, a single screw extruder, a twin screw extruder, a three screw extruder, four A melt kneader 10 such as a multi-screw extruder comprising an axial extruder and an eight-axis extruder is prepared. After the amorphous thermoplastic resin 2 is introduced into the melt kneader 10 and melted, the melt kneader is melted. The molding material 1 is prepared by newly charging the hydrophobic silica spherical fine particles 3 into the machine 10 by the side feeder method and melt-kneading with the already melted amorphous thermoplastic resin 2.

  The melt kneading machine 10 can be expected to be excellently kneaded and dispersed between the amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3, and has a vent system having a vent capable of degassing these moisture and volatile gas generated therefrom. The multi-screw extruder is preferred.

  As shown in FIG. 1, a melt kneader 10 composed of this multi-screw extruder includes a cylinder 12 installed on a pedestal 11, and a built-in shaft supported by the cylinder 12, and is rotated by driving of a motor to be amorphous. Screw 13 for extruding a strand or the like from a die 14 at the front end by melting and kneading the hydrophilic thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3, and an inlet for the amorphous thermoplastic resin 2 connected to the cylinder 12 15, a side feeder 16 for introducing hydrophobic silica spherical fine particles 3 connected to the cylinder 12, and a die 14 of the cylinder 12 that is extruded from the cooled strand to cut the cooled strand or the like to form the molding material 1. And a hot cutter 17.

  The inlet 15 and the side feeder 16 are installed as a hopper on the upper upstream side of the cylinder 12, and the side feeder 16 is configured in a screw structure and mounted on the upper downstream side of the cylinder 12. The fine hydrophobic silica spherical fine particles 3 are thrown into the side feeder 16 located downstream of the mouth 15 from the lateral direction, so that the rising of the fine hydrophobic silica spherical fine particles 3 is effectively prevented.

  When the amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3 are melt-kneaded, the melting temperature is from the glass transition point of the amorphous thermoplastic resin 2 to the glass transition point + 200 ° C., preferably the glass transition point + 80 ° C. The glass transition point + 150 ° C., more preferably glass transition point + 100 ° C. to glass transition point + 130 ° C. is preferable. This is based on the reason that the amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3 cannot be melt-kneaded and dispersed when the temperature is lower than the glass transition point of the amorphous thermoplastic resin 2. On the other hand, if the glass transition point exceeds + 200 ° C., the amorphous thermoplastic resin 2 is decomposed, which is not preferable.

  The melt-kneaded amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3 are extruded from the die 14 as a strand to be prepared as a strand molding material 1, but are extruded from the die 14 as a sheet. Thereafter, it may be prepared into a molding material 1 in the form of powder, granules, flakes or pellets. Moreover, when preparing the molding material 1, either the amorphous thermoplastic resin 2 or the hydrophobic silica spherical fine particles 3 may be dispersed in a predetermined amount or more to form a master batch.

  Next, the preparation method of (2) will be described in detail. When the amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3 are stirred and mixed by this method, a tumbler mixer, a hensil mixer, a V-type A stirring mixer such as a mixer, a Nauter mixer, a ribbon blender, or a universal stirring mixer is used.

  After the amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3 are stirred and mixed, a Banbury mixer, a mixing roll, a pressure kneader, a single screw extruder, a twin screw extruder, and a three screw extruder The molding material 1 is prepared by melt-kneading and dispersing by melt-kneading using a multi-screw extruder such as a four-screw extruder or an eight-screw extruder. Melt kneading can be expected to achieve good kneading and dispersion of amorphous thermoplastic resin 2 and hydrophobic silica spherical fine particles 3, and vent type multi-screw extrusion that can degas these moisture and volatile gas generated from these. The use of a machine is preferred. Moreover, when preparing the molding material, either the amorphous thermoplastic resin 2 or the hydrophobic silica spherical fine particles 3 may be dispersed in a predetermined amount or more to form a master batch.

  The moisture content (moisture content) of the molding material 1 before being charged into the melt extrusion molding machine 20 is adjusted to 2000 ppm or less, preferably 1000 ppm or less, more preferably 500 ppm or less by a hot air dryer or the like. This is because if the water content exceeds 2000 ppm, the amorphous thermoplastic resin film 4 may be foamed.

  When the molding material 1 is prepared, the amorphous thermoplastic resin film 4 is produced from the molding material 1, and a melt extrusion molding method, a calendar molding method, a casting method, or the like can be employed as the manufacturing method. Among these production methods, the amorphous thermoplastic resin film 4 is continuously applied from the viewpoint of improving the thickness accuracy, productivity and handling properties of the amorphous thermoplastic resin film 4 and simplifying the equipment. The melt extrusion method of extruding into a shape is optimal.

  In the melt extrusion molding method, the molding material 1 is melted and kneaded using a melt extrusion molding machine 20, and amorphous thermoplasticity is obtained from a die 23 such as a T die or a round die connected to the tip of the melt extrusion molding machine 20. In this method, the resin film 4 is continuously extruded to produce an amorphous thermoplastic resin film 4.

  As shown in FIG. 2, the melt extrusion molding machine 20 is composed of, for example, a single-screw extrusion molding machine or a twin-screw extrusion molding machine, and a raw material charging port 21 for the molding material 1 is installed above the rear portion. An inert gas supply pipe 22 that supplies an inert gas such as helium gas, neon gas, argon gas, krypton gas, and nitrogen gas as necessary is connected to the port 21. By supplying the inert gas, oxidative deterioration, oxygen crosslinking, and thermal crosslinking of the molding material 1 are effectively prevented.

  The melt temperature at the time of melt kneading of the melt extrusion molding machine 20 is a glass transition point of the amorphous thermoplastic resin 2 to a glass transition point + 200 ° C., preferably a glass transition point + 80 ° C. to a glass transition point + 150 ° C., more preferably glass. A range of transition point + 100 ° C. to glass transition point + 130 ° C. is preferable. This is because if the amorphous thermoplastic resin 2 is less than the glass transition point, the amorphous thermoplastic resin 2 and the hydrophobic silica spherical fine particles 3 cannot be melt-kneaded and dispersed. On the contrary, if the glass transition point exceeds + 200 ° C., the amorphous thermoplastic resin 2 is decomposed.

  The die 23 is connected to the front end portion of the melt extrusion molding machine 20 via a connecting pipe 24 and functions to continuously extrude the strip-shaped amorphous thermoplastic resin film 4 downward. The die 23 is preferably a T die that can obtain an amorphous thermoplastic resin film 4 with excellent thickness accuracy. A gear pump 25 mounted on the connecting pipe 24 is located upstream of the die 23, and the gear pump 25 transfers the molding material 1 to the die 23 at a constant speed and with high accuracy.

  The temperature during extrusion of the die 23 is from the glass transition point of the amorphous thermoplastic resin 2 to the glass transition point + 200 ° C., preferably the glass transition point + 80 ° C. to the glass transition point + 150 ° C., more preferably the glass transition point + 100 ° C. to A range of glass transition point + 130 ° C. is preferable. This is because the amorphous thermoplastic resin film 4 cannot be continuously extruded when it is less than the glass transition point of the amorphous thermoplastic resin 2. On the contrary, if the glass transition point exceeds + 200 ° C., the amorphous thermoplastic resin 2 is decomposed.

  The pair of crimping rolls 26 are pivotally supported below the die 23 so as to sandwich the cooling roll 27. Of the pair of crimping rolls 26, a winding tube 29 of a winder 28 that winds the amorphous thermoplastic resin film 4 is rotatably installed downstream of the downstream crimping roll 26. A slit blade 30 that forms a slit in the side portion of the amorphous thermoplastic resin film 4 is disposed between the winding tube 29 of the winder 28 so that the slit blade 30 can be moved up and down. Between the winding tube 29 of the machine 28, a necessary number of rotatable tension rolls 31 for smoothly winding the amorphous thermoplastic resin film 4 by applying tension to the amorphous thermoplastic resin film 4 are supported.

  Each crimping roll 26 is adjusted to a temperature of 50 ° C. to glass transition point + 50 ° C., preferably 100 ° C. to glass transition point, and is brought into sliding contact with the amorphous thermoplastic resin film 4 and pressed against the cooling roll 27. The reason why the temperature of the pressure roll 26 is concerned is that when the temperature is lower than 50 ° C., the pressure roll 26 is condensed. Conversely, when the glass transition point exceeds + 50 ° C., the amorphous thermoplastic resin film 4 adheres to the pressure roll 26 and breaks, or the strength of the amorphous thermoplastic resin film 4 decreases and breaks. Because there is a fear. Examples of the method for adjusting the temperature of the pressure roll 26 include a method using a heat medium such as air, water, and oil, a method using an electric heater, a method using induction heating, and the like.

  From the viewpoint of improving the adhesion between the amorphous thermoplastic resin film 4 and the cooling roll 27, at least natural rubber, isoprene rubber, butadiene rubber, norbornene rubber, acrylonitrile butadiene rubber, nitrile rubber is provided on the peripheral surface of each pressure roll 26. A rubber layer such as urethane rubber, silicone rubber, or fluorine rubber is coated as necessary, and an inorganic compound such as silica or alumina is selectively added to the rubber layer. Among these, it is preferable to select silicone rubber or fluororubber having excellent heat resistance.

  As the pressure-bonding roll 26, a metal elastic roll having a metal surface is used as necessary. When this metal elastic roll is used, the amorphous thermoplastic resin film 4 having a smooth surface can be formed. It becomes possible. Specific examples of the metal elastic roll include a metal sleeve roll, an air roll (a product name manufactured by Dimco), and a UF roll (a product name manufactured by Hitachi Zosen). Further, a pressure roll 26 whose surface is covered with a fluororesin film such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) resin or whose surface is tetrafluoroethylene-hexafluoropyrene (FEP) resin is also used. be able to.

  The cooling roll 27 is made of, for example, a metal roll having a diameter larger than that of the pressure roll 26, and the amorphous thermoplastic resin film 4 that is rotatably supported below the die 23 and is extruded between the pressure roll 26. The amorphous thermoplastic resin film 4 is cooled together with the pressure roll 26 and functions to control its thickness within a predetermined range.

  The cooling roll 27 is adjusted to a temperature of 50 ° C. to glass transition point + 50 ° C., preferably 100 ° C. to glass transition point, for the same reason as the pressure roll 26, and is in sliding contact with the amorphous thermoplastic resin film 4. Is pressed against the cooling roll 27. As a method for adjusting the temperature of the cooling roll 27, for example, a method using a heat medium such as air, water, and oil, a method using an electric heater, a method using induction heating, and the like can be used.

  When the molding material 1 is melt-extruded into a thin strip-shaped amorphous thermoplastic resin film 4, the amorphous thermoplastic resin film 4 is taken up by a pair of pressure rolls 26, a cooling roll 27, and a winder 28. The amorphous thermoplastic resin film 4 is wound around the tube 29, the both sides of the amorphous thermoplastic resin film 4 are cut with the slit blades 30 and wound around the winding tube 29 of the winder 28. Can be manufactured.

  During the production of the amorphous thermoplastic resin film 4, the amorphous thermoplastic resin film 4 may be a smooth film, but a plurality of fine particles contributing to slipperiness are provided on at least one of the front and back surfaces. It is preferable that uneven portions are formed, and each uneven portion is a concave portion having a substantially mortar shape in cross section and a convex portion having a substantially hollow truncated cone shape. The uneven portions may be regularly arranged in a zigzag shape or irregularly as necessary.

  As a method of forming a plurality of fine uneven portions on the amorphous thermoplastic resin film 4, (1) forming fine uneven portions on the peripheral surfaces of the pair of pressure-bonding rolls 26 and the cooling roll 27, respectively, A method of transferring an uneven portion by sandwiching an amorphous thermoplastic resin film 4 between a pressure roll 26 and a cooling roll 27; (2) fine zirconia, glass, stainless steel, etc. on the amorphous thermoplastic resin film 4; A method of transferring fine irregularities by spraying inorganic compounds, polycarbonate, nylon, plant seeds, etc., and (3) pressing an amorphous thermoplastic resin film 4 with a mold having fine irregularities. And a method of transferring and forming fine uneven portions.

  Among these methods, from the viewpoints of simplification of equipment for forming the concavo-convex portion, accuracy of the size of the concavo-convex portion, uniform formation of the concavo-convex portion, easy formation of the concavo-convex portion, formation of continuous concavo-convex portions, The method (1) is optimal. In this case, the cooling roll 27 is preferably an etching roll instead of a sandblast roll so that the corners of the concavo-convex portion are not angular.

  The surface roughness of the amorphous thermoplastic resin film 4 on which fine irregularities are formed is 0.01 to 0.50 μm, preferably 0.05 to 0.30 μm in terms of arithmetic average roughness (Ra). is there. This is based on the reason that when the arithmetic average roughness (Ra) exceeds 0.50 μm, the mechanical properties of the amorphous thermoplastic resin film 4 are deteriorated, and there is a possibility of breaking during melt extrusion molding. In addition, since the dielectric breakdown voltage decreases, it is based on the reason that it cannot be used as a base film for a film capacitor.

The amorphous thermoplastic resin film 4 cooled and manufactured by the cooling roll 27 has a slip coefficient of 1 in terms of a static friction coefficient (μs) from the viewpoint of satisfying slipperiness, mechanical characteristics, electrical characteristics, heat resistance and the like. 0.0 or less, dynamic friction coefficient (μk) of 1.0 or less, mechanical properties of tensile strength of 50 N / mm ² or more, elongation at break of 50% or more, heat resistance of storage elastic modulus (E ′) The inflection point temperature is 200 ° C. or higher. In addition, the dielectric breakdown voltage is set to 250 V / μm or more from the viewpoint of satisfying electrical characteristics when used as a base film for a film capacitor. Furthermore, in order to satisfy the acoustic characteristics when used as a base film for a diaphragm of a speaker, the acoustic characteristics are set to 0.015 or more at a loss tangent at 20 ° C.

  According to the above, since the hydrophobic silica spherical fine particles 3 are contained in the molding material 1, the slipperiness of the amorphous thermoplastic resin film 4 can be greatly improved. Further, since the average particle diameter of the hydrophobic silica spherical fine particles 3 is in the range of 5 nm to 1000 nm, the uniform dispersibility and fluidity are good, and the slipperiness and mechanical strength can be improved. Further, since the amorphous thermoplastic resin 2 having a glass transition point of 200 ° C. or higher is used as the molding material 1 instead of the simple amorphous thermoplastic resin 2, the improvement in heat resistance is greatly expected. it can.

  In the above embodiment, the screw-type side feeder 16 is connected to the cylinder 12 of the melt-kneader 10. However, the present invention is not limited to this, and the hopper-structure side feeder 16 may be connected. Moreover, although the several uneven | corrugated | grooved part which contributes to slidability was formed in the amorphous thermoplastic resin film 4, as long as slidability can be ensured, even if it forms a recessed part or a convex part instead of an uneven | corrugated part. good.

Examples of the method for producing an amorphous thermoplastic resin film according to the present invention will be described below together with comparative examples.
[Example 1]
First, 100 parts by mass of a polyetherimide resin having a glass transition point of 210 ° C. (product name: ULTEM 9011-1000-NB, manufactured by SABIC Innovative Plastics Co., Ltd.) is charged into a raw material charging port of a co-rotating twin screw extruder and melted. Then, hydrophobic silica spherical fine particles (product name: X-24-9163A manufactured by Shin-Etsu Chemical Co., Ltd.) having an average particle size of 110 nm were added to the die-side side feeder of the same-direction rotating twin-screw extruder with 100 mass of polyetherimide resin By supplying 0.5 parts by mass with respect to the part, melt-kneading and dispersing, extruding the melt-kneaded product from a die at the tip of the same-direction rotating twin-screw extruder in a rod shape and cutting with a pelletizer after water cooling A pellet-shaped molding material was prepared.

  The glass transition point (Tg) of the polyetherimide resin is determined by using a differential scanning calorimeter [product name: high-sensitivity differential scanning calorimeter X-DSC7000] manufactured by SII Nano Technologies, Inc. in accordance with JISK7121. The measurement was performed at 10 ° C./min. Further, the polyetherimide resin and the hydrophobic silica spherical fine particles are a vent on the raw material inlet side of the co-rotating twin screw extruder under conditions of a cylinder temperature of 340 ° C. and a die temperature of 340 ° C. of the co-rotating twin screw extruder. The mixture was melt-kneaded in an open state to prepare a molding material. It was 371 degreeC when the temperature at the time of melt-kneading was measured from the temperature of die | dye.

  In addition, polyether imide resin (product name: ULTEM 9011-1000-NB manufactured by SABIC Innovative Plastics) having a glass transition point of 210 ° C. is hereinafter abbreviated as 9011-1000.

  Next, the prepared molding material was put into a dehumidifying hot air dryer (product name: Multijet MJ3, manufactured by Matsui Seisakusho Co., Ltd.) heated to 150 ° C. and dried for 12 hours, and the moisture content of the dried molding material was 300 ppm or less. After confirming the above, the molding material was put into a single screw extruder having a diameter of 40 mm and continuously extruded from a T die having a width of 900 mm to form a band-shaped amorphous thermoplastic resin film. The moisture content of the molding material was confirmed by the Karl Fischer titration method using a trace moisture measuring device (product name: CA-100 manufactured by Mitsubishi Chemical Corporation). Thereafter, the moisture content of the molding material was measured by the same method.

  When charging the molding material into the single screw extruder, nitrogen gas 18 L / min was supplied. In addition, the single screw extruder was L / D = 32, compression ratio: 2.5, screw: full flight screw. The cylinder temperature of this single screw extruder is 310 to 360 ° C, the temperature of the T die is 360 to 365 ° C, the temperature of the connecting pipe connecting the single screw extruder and the T die is 360 ° C, and the gear pump is 365 ° C. It was adjusted. It was 342 degreeC when the temperature of the fuse | melted molding material was measured from the resin temperature of T-die inlet_port | entrance.

  Once the amorphous thermoplastic resin film is formed, the both sides of the continuous amorphous thermoplastic resin film are cut with a slit blade and wound into a take-up tube in order to obtain an amorphous material having a length of 100 m and a width of 620 mm. A thermoplastic resin film was produced. The amorphous thermoplastic resin film is sequentially wound around a pair of pressure-bonding rolls having silicone rubber on the peripheral surface, a metal roll as a cooling roll, and a 6-inch winding tube located downstream of these rolls. A plurality of fine irregularities were formed on both the front and back surfaces of the amorphous thermoplastic resin film by being sandwiched between metal rolls.

  The arithmetic average roughness (Ra) of the silicone rubber of each crimping roll was 0.44 to 0.47 μm. Moreover, as a metal roll, the 150 degreeC etching roll provided with the convex pattern whose arithmetic mean roughness (Ra) is 1.28 micrometers on the surrounding surface was used.

  Once the amorphous thermoplastic resin film is manufactured, the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of the amorphous thermoplastic resin film are evaluated. Are summarized in Table 1. The surface roughness of the amorphous thermoplastic resin film is the arithmetic average roughness (Ra), the slip property is the static friction coefficient (μs) and the dynamic friction coefficient (μk), the mechanical properties are the tensile strength and the elongation at break, and the heat resistance is The first inflection point temperature of the storage elastic modulus (E ′), electrical characteristics were evaluated by dielectric breakdown voltage, and acoustic characteristics were evaluated by loss tangent.

-Film thickness About the thickness of the amorphous thermoplastic resin film whose film thickness is 3-10 micrometers, the contact-type thickness meter [The product name: Marimar 1240 made from Marh company attached the Millimar Inductive Probe 1301 Marh-LVDT to the compact amplifier. Apparatus]. On the other hand, the thickness of an amorphous thermoplastic resin film having a film thickness exceeding 10 μm and up to 150 μm was measured using a micrometer (product name: coolant proof micrometer code MDC-25PJ manufactured by Mitutoyo Corporation). did.

  In the measurement, 100 predetermined thicknesses where the extrusion direction and the width direction (perpendicular direction to the extrusion direction) of the amorphous thermoplastic resin film intersect were measured, and the average value was taken as the film thickness. The measurement locations in the extrusion direction were 100 mm, 200 mm, 300 mm, 400 mm, and 500 mm at 100 mm intervals from the tip of the amorphous thermoplastic resin film. On the other hand, the measurement location in the width direction is 25 mm from the left end of the amorphous thermoplastic resin film, then 55 mm, 85 mm, 115 mm, 145 mm, 175 mm, 205 mm, 235 mm, 265 mm, 295 mm, 325 mm, 355 mm, at 30 mm intervals. The locations were 385 mm, 415 mm, 445 mm, 475 mm, 505 mm, 535 mm, 565 mm, and 595 mm.

-Surface property of an amorphous thermoplastic resin film About the surface property of the amorphous thermoplastic resin film, the surface of the amorphous thermoplastic resin film was touched with a finger, and the tactile sensation was evaluated. Specifically, the case where the surface of the amorphous thermoplastic resin film was smooth was marked with ◯, and the case where the surface of the amorphous thermoplastic resin film was rugged was marked with ×.

-Surface roughness of the amorphous thermoplastic resin film The surface roughness of the amorphous thermoplastic resin film was evaluated by arithmetic average roughness (Ra). Specifically, according to JIS B0601-2001, the pressure-bonding roll surface side and the cooling roll surface side were measured in the longitudinal direction (extrusion direction) of the amorphous thermoplastic resin film.

・ Sliding property of amorphous thermoplastic resin film (sliding property between amorphous thermoplastic resin films)
The slipperiness of the amorphous thermoplastic resin film was evaluated by a static friction coefficient and a dynamic friction coefficient. The static friction coefficient and the dynamic friction coefficient were measured according to JIS K7125-1999. Specifically, using a surface property measuring instrument (product name: HEDON-14 manufactured by Shinto Kagaku Co., Ltd.) in an environment of 23 ° C. and 50% RH, the test speed is 100 mm / min, the load is 200 g, and the contact area is 63.5 mm. It measured on the conditions of * 63.5mm. And under this condition, the cooling roll surface side of the amorphous thermoplastic resin film is fixed to the moving table side, the pressure roll side of the amorphous thermoplastic resin film is fixed to the flat indenter side, and a load of 200 g is applied. Test speed: The static friction coefficient and the dynamic friction coefficient were measured at 100 mm / min.

・ Sliding property of amorphous thermoplastic resin film (sliding property between amorphous thermoplastic resin film and polycarbonate resin film)
The slipping property between the amorphous thermoplastic resin film and the polycarbonate resin film was also evaluated by the static friction coefficient and the dynamic friction coefficient. As the polycarbonate resin film, a commercially available polycarbonate resin film having a thickness of 0.5 mm (product name: PCSMPS610 polycarbonate / transparent, manufactured by Takiron Co., Ltd.) was used.

  The static friction coefficient and the dynamic friction coefficient were measured in accordance with JIS K7125-1299. Specifically, using a surface property measuring instrument (product name: HEDON-14 manufactured by Shinto Kagaku Co., Ltd.) in an environment of 23 ° C. and 50% RH, the test speed is 100 mm / min, the load is 200 g, and the contact area is 63.5 mm. It measured on the conditions of * 63.5mm. And under this condition, the cooling roll surface side of the amorphous thermoplastic resin film is fixed to the moving table side, the pressure roll side of the amorphous thermoplastic resin film is fixed to the flat indenter side, and a load of 200 g is applied. Test speed: The static friction coefficient and the dynamic friction coefficient were measured at 100 mm / min.

-Mechanical properties of amorphous thermoplastic resin film The mechanical properties of the amorphous thermoplastic resin film were evaluated by tensile strength and tensile elongation at break. Specifically, in the environment of 23 ° C. and 50% RH, the extrusion direction and the width direction were measured at a tensile speed of 50 mm / min according to JIS K6781. The maximum strength was measured as the tensile strength.

-Heat resistance of amorphous thermoplastic resin film The heat resistance of the amorphous thermoplastic resin film was evaluated by the first inflection point temperature of the storage elastic modulus (E '). The storage elastic modulus of the amorphous thermoplastic resin film was measured in the extrusion direction and the width direction (the direction perpendicular to the extrusion direction) of the amorphous thermoplastic resin film. Specifically, when measuring the storage elastic modulus in the extrusion direction of the amorphous thermoplastic resin film, the storage elastic modulus in the width direction of the amorphous thermoplastic resin film is measured. When doing, it cut out and measured to the magnitude | size of extrusion direction 6mm x width direction 60mm.

  When measuring the storage elastic modulus, a frequency mode of 1 Hz, a strain of 0.1%, and a rate of temperature increase were determined by a tensile mode using a viscoelastic spectrometer [product name: RSA-G2 manufactured by TS Instruments Japan Co., Ltd.]. The measurement was performed under the conditions of 3 ° C./min, measurement temperature range −60 ° C. to 300 ° C., and check interval 21 mm.

  As shown in FIG. 3, the first inflection point temperature was the temperature at the intersection where two linear portions with respect to the storage elastic modulus change curve were extended. When determining the first inflection point temperature, first, the straight line portion before the first sudden drop in the storage elastic modulus is extended to the high temperature side to draw the first straight line a, and the storage elastic modulus is first suddenly increased. The straight line after dropping to the lower side is extended to draw the second straight line b, and then the vertical line at the intersection of both lines a and b is drawn to the horizontal temperature axis, and the temperature is changed to the first inflection. A point temperature was used.

-Electrical characteristics of the amorphous thermoplastic resin film The electrical characteristics of the amorphous thermoplastic resin film were evaluated by dielectric breakdown voltage. The dielectric breakdown voltage was measured in a short-time dielectric breakdown test by an air method according to JIS C2110-1994. Specifically, the dielectric breakdown voltage was measured from the cooling roll surface side in an environment of 23 ° C. and evaluated. The dielectric breakdown tester used was a withstand voltage / insulation resistance tester (product name: TOS9201 manufactured by Kikusui Electronics Co., Ltd.), and the air test electrode device (product name: TJ-20 manufactured by Tama Denso Co., Ltd.) was used as the electrode. The shape of the electrode was a cylinder (upper shape diameter 25 mm, height 25 mm, lower shape diameter 25 mm, height 15 mm).
Since the measurement upper limit value of the dielectric breakdown tester is 6100V, the electrical characteristics of the amorphous thermoplastic resin film reaching 6100V were not evaluated.

-Acoustic characteristics of the amorphous thermoplastic resin film The acoustic characteristics of the amorphous thermoplastic resin film were evaluated by loss tangent at 20 ° C. The loss tangent of the amorphous thermoplastic resin film was measured in the extrusion direction and the width direction (the direction perpendicular to the extrusion direction) of the amorphous thermoplastic resin film.

  Specifically, when measuring the loss tangent in the extrusion direction of the amorphous thermoplastic resin film, the extrusion direction is 60 mm × 6 mm in the width direction, and when measuring the loss tangent in the width direction, the extrusion direction is 6 mm × width. Measurement was performed by cutting out to a size of 60 mm in the direction. In the measurement, a tension mode using a viscoelastic spectrometer [product name: RSA-G2 manufactured by TS Instruments Japan Co., Ltd.] was used, and the frequency was 1 Hz, the strain was 0.1%, and the heating rate was 3 ° C./min. The measurement temperature range was −60 ° C. to 300 ° C. and the check interval was 21 mm.

[Example 2]
Basically the same as in Example 1, but the addition amount of the hydrophobic silica spherical fine particles was changed to 1.0 part by mass with respect to 100 parts by mass of the polyetherimide resin. When the melt kneading temperature of the polyetherimide resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1, it was 376 ° C. Further, the temperature when the molding material was charged in a φ40 mm single screw extruder and melted was 343 ° C.
Once the amorphous thermoplastic resin film is manufactured, the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of the amorphous thermoplastic resin film are evaluated. Are summarized in Table 1.

Example 3
Basically the same as in Example 1, but the addition amount of the hydrophobic silica spherical fine particles was changed to 5.0 parts by mass with respect to 100 parts by mass of the polyetherimide resin. When the melt kneading temperature of the polyetherimide resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1, it was 376 ° C. Further, the temperature when the molding material was charged in a φ40 mm single screw extruder and melted was 346 ° C. The metal roll was changed to a 180 ° C. etching roll having a convex pattern with an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.

  Once the amorphous thermoplastic resin film is manufactured, the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of the amorphous thermoplastic resin film are evaluated. Are summarized in Table 1.

Example 4
Basically the same as in Example 1, but the addition amount of the hydrophobic silica spherical fine particles was changed to 10 parts by mass with respect to 100 parts by mass of the polyetherimide resin. The melt kneading temperature of the polyetherimide resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1. As a result, it was 372 ° C. Further, the temperature when the molding material was charged in a φ40 mm single screw extruder and melted was 341 ° C. The metal roll was changed to a 210 ° C. etching roll provided with a convex pattern having an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.

  After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Are summarized in Table 1. However, since the dielectric breakdown voltage of the amorphous thermoplastic resin film reached 6100 V, the dielectric breakdown voltage of the amorphous thermoplastic resin film was not evaluated.

Example 5
A polyetherimide resin having a glass transition point of 211 ° C. [Product name: ULTEM 1010-1000-NB, manufactured by SABIC Innovative Plastics Co., Ltd.] was introduced into a raw material inlet of a co-rotating twin screw extruder and melted. Hydrophobic silica spherical fine particles (product name: X-24-9404, manufactured by Shin-Etsu Chemical Co., Ltd.) having an average particle diameter of 35 nm are added to 100 parts by mass of polyetherimide resin on the side feeder on the die side of the same-direction rotating twin-screw extruder. Pellets are supplied to 5.0 parts by weight, melt-kneaded and dispersed, and the melt-kneaded product is extruded from a die at the tip of a co-rotating twin-screw extruder in a rod shape and cut with a pelletizer after water cooling. A shaped molding material was prepared. The melt kneading temperature of the polyetherimide resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1 and found to be 379 ° C.

In addition, a polyetherimide resin (product name: ULTEM 1010-1000-NB manufactured by SABIC Innovative Plastics) having a glass transition point of 211 ° C. is hereinafter abbreviated as 1010-1000.
Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the temperature when the molding material was poured into a φ40 mm single screw extruder and melted was 340 ° C. . Further, the metal roll was changed to an etching roll of 210 ° C. having a convex pattern with an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.

  After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 2 shows the results. However, since the dielectric breakdown voltage of the amorphous thermoplastic resin film reached 6100 V, the dielectric breakdown voltage of the amorphous thermoplastic resin film was not evaluated.

Example 6
100 parts by mass of the polyetherimide resin of Example 5 was charged into a raw material inlet of a co-rotating twin screw extruder and melted, and the average particle diameter was 77 nm in the side feeder on the die side of the co-rotating twin screw extruder. Hydrophobic silica spherical fine particles (manufactured by Shin-Etsu Chemical Co., Ltd., product name: X-24-9600-80) are supplied so as to be 3.0 parts by mass with respect to 100 parts by mass of the polyetherimide resin, and melt kneaded and dispersed. Then, the melt-kneaded product was extruded from a die at the tip of the same-direction rotating twin-screw extruder into a rod shape, cooled with water, and cut with a pelletizer to prepare a pellet-shaped molding material. The melt kneading temperature of the polyetherimide resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1 and found to be 375 ° C.

Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the temperature when the molding material was put into a φ40 mm single screw extruder and melted was 342 ° C. . Moreover, the metal roll was changed to the etching roll of 180 degreeC which equipped the surrounding surface with the convex pattern whose arithmetic mean roughness (Ra) is 1.28 micrometers.
After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 2 shows the results.

Example 7
100 parts by mass of a polyetherimide resin having a glass transition point of 222 ° C. [Product name: ULTEM CRS5001-1000-NB] manufactured by SABIC Innovative Plastics Co., Ltd. is introduced into a raw material inlet of a co-rotating twin-screw extruder and melted. Supplying the hydrophobic silica spherical fine particles of Example 6 to 15 parts by mass with respect to 100 parts by mass of the polyetherimide resin to the side feeder on the die side of the same-direction rotating twin-screw extruder, and melt-kneading and dispersing. The melt-kneaded material was extruded in the shape of a rod from a die at the tip of the same-direction rotating twin-screw extruder, cooled with water, and then cut with a pelletizer to prepare a pellet-shaped molding material.

The cylinder temperature of the co-rotating twin screw extruder was changed to 350 ° C., and the die temperature was changed to 350 ° C. The melt kneading temperature of the polyetherimide resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1, and found to be 385 ° C.
In addition, polyetherimide resin (product name: ULTEM CRS5001-1000-NB manufactured by SABIC Innovative Plastics) having a glass transition point of 222 ° C. is hereinafter abbreviated as CRS5001-1000.

  Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the cylinder temperature of the single screw extruder was 310 to 370 ° C., the temperature of the T die was 370 to 375 ° C., and the single screw extruder. The temperature of the connecting pipe connecting the dies and the T dice was changed to 370 ° C., and the gear pump was changed to 375 ° C. It was 353 degreeC when the temperature when a molding material was thrown into the single screw extruder of (phi) 40 mm and was fuse | melted was measured. Further, the metal roll was changed to an etching roll of 210 ° C. having a convex pattern with an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.

  After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 2 shows the results. However, since the dielectric breakdown voltage of the amorphous thermoplastic resin film reached 6100 V, the dielectric breakdown voltage of the amorphous thermoplastic resin film was not evaluated.

Example 8
Polyether sulfone resin with a glass transition point of 220 ° C. (product name Veradel polyether sulfone A-301NT, manufactured by Solvay Specialty Polymers Co., Ltd.) 100 parts by mass is charged into the raw material inlet of a co-rotating twin screw extruder and melted And supply the hydrophobic silica spherical fine particles of Example 1 to 3.0 parts by mass with respect to 100 parts by mass of the polyethersulfone resin to the side feeder on the die side of the same-direction rotating twin-screw extruder. The melt-kneaded material was dispersed, and the melt-kneaded product was extruded from a die at the tip of the same-direction rotating twin-screw extruder into a rod shape and then cooled with water and cut with a pelletizer to prepare a pellet-shaped molding material.

The cylinder temperature of the co-rotating twin screw extruder was changed to 350 ° C., and the die temperature was changed to 350 ° C. When the melt kneading temperature of the polyethersulfone resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1, it was 383 ° C.
The polyether sulfone resin having a glass transition point of 220 ° C. (product name Veradel polyether sulfone A-301NT manufactured by Solvay Specialty Polymers) is hereinafter abbreviated as A-301NT.

  Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the cylinder temperature of the single screw extruder was 310 to 370 ° C., the temperature of the T die was 370 to 375 ° C., and the single screw extruder. The temperature of the connecting pipe connecting the dies and the T dice was changed to 370 ° C., and the gear pump was changed to 375 ° C. It was 355 degreeC when the temperature when a molding material was injected | thrown-in to the single screw extruder of (phi) 40mm and was fuse | melted was measured. The metal roll was changed to a 150 ° C. etching roll having a convex pattern with an arithmetic average roughness (Ra) of 1.28 μm on the peripheral surface.

  After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 2 shows the results.

Example 9
100 parts by weight of polyphenylsulfone resin (product name Radel Polyphenylsulfone R-5000NT, manufactured by Solvay Specialty Polymers Co., Ltd.) having a glass transition point of 218 ° C. is charged into the raw material inlet of a co-rotating twin screw extruder and melted. Then, the hydrophobic silica spherical fine particles of Example 1 are supplied to the side feeder on the die side of the same-direction rotating twin-screw extruder so as to be 1.0 part by mass with respect to 100 parts by mass of the polyphenylsulfone resin and melted. A pellet-shaped molding material was prepared by kneading and dispersing, and extruding the melt-kneaded material in a rod shape from a die at the tip of the same-direction rotating twin-screw extruder, followed by water cooling and cutting with a pelletizer.

The cylinder temperature of the co-rotating twin screw extruder was 350 ° C., and the die temperature was 350 ° C. When the melt kneading temperature of the polyphenylsulfone resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1, it was 380 ° C.
The polyphenylsulfone resin having a glass transition point of 218 ° C. (product name Radel polyphenylsulfone R-5000NT manufactured by Solvay Specialty Polymers) is hereinafter abbreviated as R-5000NT.

  Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the cylinder temperature of the single screw extruder was 310 to 370 ° C., the temperature of the T die was 370 to 375 ° C., and the single screw extruder. The temperature of the connecting pipe connecting the dies and the T dice was changed to 370 ° C., and the gear pump was changed to 375 ° C. It was 355 degreeC when the temperature when a molding material was injected | thrown-in to the single screw extruder of (phi) 40mm and was fuse | melted was measured. Further, the metal roll was changed to an etching roll of 210 ° C. having a convex pattern with an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.

  After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 3 shows the results. However, since the dielectric breakdown voltage of the amorphous thermoplastic resin film reached 6100 V, the dielectric breakdown voltage of the amorphous thermoplastic resin film was not evaluated.

[Comparative Example 1]
100 parts by mass of the polyetherimide resin of Example 1 is charged into a raw material charging port of a co-rotating twin-screw extruder and melted, and the hydrophobic side of Example 1 is fed to the side feeder on the die side of the co-rotating twin-screw extruder. The spherical silica fine particles are supplied so as to be 0.02 parts by mass with respect to 100 parts by mass of the polyetherimide resin, and are melt-kneaded and dispersed, and the melt-kneaded product is formed into a rod shape from the die at the tip of the co-rotating twin-screw extruder. Pellet-shaped molding material was prepared by extruding into water and then cooling with water and cutting with a pelletizer. The melt kneading temperature of the polyetherimide resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1 and found to be 370 ° C.

Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the temperature when the molding material was poured into a single screw extruder of φ40 mm and melted was 343 ° C. . The metal roll was changed to a 150 ° C. etching roll having a convex pattern with an arithmetic average roughness (Ra) of 1.28 μm on the peripheral surface.
After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 4 shows the results.

[Comparative Example 2]
100 parts by mass of the polyetherimide resin of Example 1 is charged into a raw material charging port of a co-rotating twin-screw extruder and melted, and the hydrophobic side of Example 1 is fed to the side feeder on the die side of the co-rotating twin-screw extruder. The spherical silica fine particles are supplied so as to be 25 parts by mass with respect to 100 parts by mass of the polyetherimide resin, and are melt-kneaded and dispersed, and the melt-kneaded product is extruded into a rod shape from the die at the tip of the same-direction rotating twin-screw extruder. After cooling with water, the pellet-shaped molding material was prepared by cutting with a pelletizer. The melt kneading temperature of the polyetherimide resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1. As a result, it was 373 ° C.

Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1. The temperature at which the molding material was charged in a φ40 mm single screw extruder and melted was 347 ° C. . The metal roll was changed to a 180 ° C. etching roll having a convex pattern with an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.
After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 4 shows the results.

[Comparative Example 3]
100 parts by mass of the polyethersulfone resin of Example 8 is charged into a raw material charging port of the same-direction rotating twin screw extruder and melted, and the side feeder on the die side of the same direction rotating twin-screw extruder is used. Hydrophobic silica spherical fine particles are supplied in an amount of 0.05 parts by mass with respect to 100 parts by mass of the polyethersulfone resin, and are melt-kneaded and dispersed. A pellet-shaped molding material was prepared by extruding into a rod shape and cutting with a pelletizer after water cooling. When the melt kneading temperature of the polyethersulfone resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1, it was 381 ° C.

Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the temperature when the molding material was poured into a φ40 mm single screw extruder and melted was 348 ° C. . The metal roll was changed to a 150 ° C. etching roll having a convex pattern with an arithmetic average roughness (Ra) of 1.28 μm on the peripheral surface.
After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 4 shows the results.

[Comparative Example 4]
100 parts by mass of the polyphenylsulfone resin of Example 9 was introduced into the raw material inlet of the same-direction rotating twin-screw extruder and melted, and the side feeder on the die side of the same-direction rotating twin-screw extruder was fed to the side feeder of Example 1. Hydrophobic silica spherical fine particles are supplied so as to be 25 parts by mass with respect to 100 parts by mass of the polyphenylsulfone resin, and are melt-kneaded and dispersed. Pellet-shaped molding material was prepared by extruding into water and then cooling with water and cutting with a pelletizer. The melt kneading temperature of the polyphenylsulfone resin and the hydrophobic silica spherical fine particles was measured in the same manner as in Example 1 and found to be 386 ° C.

Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the temperature when the molding material was put into a φ40 mm single screw extruder and melted was 359 ° C. . Further, the metal roll was changed to an etching roll of 210 ° C. having a convex pattern with an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.
After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 4 shows the results.

[Comparative Example 5]
100 parts by mass of the polyetherimide resin of Example 1 was charged into a raw material charging port of a co-rotating twin screw extruder and melted, and an average particle size of 6 was provided on the side feeder on the die side of the co-rotating twin screw extruder. .4 nm spherical silica fine particles [manufactured by Admatechs, product name: 5 μm-E1] are supplied so as to be 5.0 parts by mass with respect to 100 parts by mass of the polyetherimide resin, and are melt-kneaded and dispersed. Was extruded in the shape of a rod from the die at the tip of the same-direction rotating twin-screw extruder, cooled with water, and then cut with a pelletizer to prepare a pellet-shaped molding material. When the melt kneading temperature of the polyetherimide resin and the spherical silica fine particles was measured in the same manner as in Example 1, it was 369 ° C.

Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the temperature when the molding material was put into a φ40 mm single screw extruder and melted was 341 ° C. . The metal roll was changed to a 180 ° C. etching roll having a convex pattern with an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.
After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 5 shows the results. However, since the dielectric breakdown voltage of the amorphous thermoplastic resin film reached 6100 V, the dielectric breakdown voltage of the amorphous thermoplastic resin film was not evaluated.

[Comparative Example 6]
100 parts by mass of the polyetherimide resin of Example 1 was charged into a raw material charging port of a co-rotating twin screw extruder and melted, and the average particle diameter was 0 on the side feeder on the die side of the co-rotating twin screw extruder. .07 μm synthetic calcium carbonate [Specialty Minerals Inc. Co., Ltd. product name: MULTIFEX-MM] is supplied so as to be 10 parts by mass with respect to 100 parts by mass of the polyetherimide resin, and is melt-kneaded and dispersed. A pellet-shaped molding material was prepared by extruding from a die into a rod shape and cooling with water and then cutting with a pelletizer. It was 372 degreeC when the melt-kneading temperature of polyetherimide resin and synthetic calcium carbonate was measured similarly to Example 1. FIG.

Hereinafter, an amorphous thermoplastic resin film was produced in the same manner as in Example 1, but the temperature when the molding material was poured into a single screw extruder of φ40 mm and melted was 343 ° C. . The metal roll was changed to a 150 ° C. etching roll having a convex pattern with an arithmetic average roughness (Ra) of 1.86 μm on the peripheral surface.
After manufacturing the amorphous thermoplastic resin film, evaluate the film thickness, surface condition, surface roughness, slipperiness, mechanical properties, heat resistance, electrical properties, and acoustic properties of this amorphous thermoplastic resin film. Table 5 shows the results.

[Result]
The amorphous thermoplastic resin film of each example has a tensile strength of 80 N / mm ² or more, an elongation at tensile break of 90% or more, and heat resistance (first inflection point temperature of storage elastic modulus (E ′)). Is at least 200 ° C., electrical characteristics are 250 V / μm or more in terms of breakdown voltage, and acoustic characteristics are at least 0.015 in terms of loss tangent at 20 ° C., and are excellent in mechanical characteristics, heat resistance, electrical characteristics, and acoustic characteristics. It was. Further, the slipperiness was 1.0 or less in terms of static friction coefficient (μs) and dynamic friction coefficient (μk), and excellent slipperiness could be obtained.

On the other hand, the amorphous thermoplastic resin films of Comparative Examples 1 and 3 are excellent in mechanical properties, heat resistance, electrical properties, and acoustic properties, but can adhere to each other and obtain slipperiness. There wasn't.
The amorphous thermoplastic resin films of Comparative Examples 2 and 4 had a slipperiness of 1.0 or less in terms of the static friction coefficient (μs) and the dynamic friction coefficient (μk), and an excellent slipperiness could be obtained. Moreover, heat resistance was 200 degreeC or more, and it was excellent also in heat resistance. However, the tensile strength is less than 50 N / mm ² , the elongation at break at break is less than 50%, the electrical characteristics are less than 200 V / μm in breakdown voltage, and the acoustic characteristics are less than 0.015 in loss tangent at 20 ° C. The mechanical characteristics, electrical characteristics, and acoustic characteristics were insufficient.

The amorphous thermoplastic resin films of Comparative Examples 5 and 6 had slip properties of 1.0 or less in terms of static friction coefficient (μs) and dynamic friction coefficient (μk), and excellent slip properties were obtained. Further, the heat resistance was 200 ° C. or higher, and the acoustic characteristics were 0.015 or more at a loss tangent at 20 ° C., and excellent heat resistance and acoustic characteristics could be obtained. However, the film surface was rugged and the smoothness was extremely insufficient. Moreover, the tensile strength was less than 50 N / mm ² , the elongation at break at break was less than 50%, the electrical characteristics were less than 200 V / μm in terms of dielectric breakdown voltage, and the mechanical and electrical characteristics were insufficient.

  The method for producing an amorphous thermoplastic resin film according to the present invention is used in the field of resin film production.

DESCRIPTION OF SYMBOLS 1 Molding material 2 Amorphous thermoplastic resin 3 Hydrophobic silica spherical fine particle 4 Amorphous thermoplastic resin film 10 Melt kneading machine 15 Input port 16 Side feeder 20 Melt extrusion molding machine (extrusion molding machine)
23 Die 26 Crimp roll 27 Cooling roll 29 Winding tube

Claims (4)

A method for producing an amorphous thermoplastic resin film for producing an amorphous thermoplastic resin film having a glass transition point of 200 ° C. or higher by a molding method using a predetermined resin-containing molding material,
The molding material contains 100 parts by mass of an amorphous thermoplastic resin having a glass transition point of 200 ° C. or higher, and 0.1 to 20 parts by mass of hydrophobic silica spherical fine particles, and has a water content of 2000 ppm or less,
The molding material is put into an extrusion machine for film, and an amorphous thermoplastic resin film is continuously melt-extruded from the die, and the temperature of the extruder and the die during the melt-extrusion molding is changed to amorphous. The glass transition point of the thermoplastic resin to the glass transition point + 200 ° C., and the melt-extruded amorphous thermoplastic resin film is wound around a pressure roll, a cooling roll, and a winding tube located downstream of these, A method for producing an amorphous thermoplastic resin film, characterized in that the temperature of at least one of the pressure roll and the cooling roll is in the range of 50 ° C to the glass transition point of the amorphous thermoplastic resin + 50 ° C. .   An amorphous thermoplastic resin having a glass transition point of 200 ° C. or higher is introduced into a melt kneader for molding material and melted. Then, spherical silica fine particles are introduced into the melt kneader to produce amorphous heat. The method for producing an amorphous thermoplastic resin film according to claim 1, wherein a molding material is prepared by melt-kneading with a plastic resin, and then the prepared molding material is put into an extruder for film.   The melt kneader for molding material is provided with an inlet for an amorphous thermoplastic resin, and a side feeder for introducing hydrophobic silica spherical fine particles located downstream from the inlet. A process for producing an amorphous thermoplastic resin film. The slip of the amorphous thermoplastic resin film cooled by the cooling roll is set to 1.0 or less in terms of the static friction coefficient (μs), 1.0 or less in terms of the dynamic friction coefficient (μk), and the mechanical properties are set to 50 N in terms of tensile strength. / Mm ² or more, 50% or more in elongation at tensile break, heat resistance at 200 ° C. or more at the first inflection point of storage modulus (E ′), and electrical characteristics at 250 V / μm or more in dielectric breakdown voltage The method for producing an amorphous thermoplastic resin film according to claim 1, 2, or 3, wherein the acoustic characteristics are 0.015 or more in loss tangent at 20 ° C.

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